Ink from nylon, cresylic acid, and pigment



United States Patent O1 3,303,160 INK FROM NYLON, CRESYLIC ACID, AND PEGMENT Robert K. Renter, Evanston, Ill., assignor to Inca Inks,

Inc, Evanstou, Ill., a corporation of Illinois No Drawing. Filed July 17, 1961, Ser. No. 124,329 1 Claim. (Cl. 2ss 3s.4

My invention relates to improvements and innovations in compositions for use in printing and coating. More particularly, it relates to such compositions for use in practicing the process and using the apparatus disclosed in my co-pending application, Serial No. 846,750, filed October 15, 1959, now Patent No. 3,067,056, of which the present application is a continuation-in-part.

A-cording to my prior application an ink or coating composition is dissolved in a volatile solvent which is retained in the lower portion of a tank or in a fountain. Means are provided in the bottom of the tank or fountain for controlling the temperature of the bath or solvent at approximately the boiling point thereof. An etched or mechanically knurled printing cylinder is mounted in the tank or fountain so as to run in the bath at the proper depth. The web or sheet material being treated is passed through the intaglio or rotogravure printing or coating unit located in the lower part of the fountain and thereby receives a metered surface deposit of the ink or coating in the form of tiny dots characteristic of intaglio or rotogravure printing. Since the temperature is maintained at or near the boiling point in the vicinity of the applicating cylinder, the volatile solvent is immediately vaporized, leaving behind a metered deposit of the ink or coating composition on the surface of the web in which the dots have become merged or joined into a continuous film on the surface. The upper portion of the tank or fountain extends above the printing or coating unit so as to retain the vapors therein and is provided with condensing means for condensing the solvent vapors so as to recover the same and prevent them from leaving the fountain. The web or sheet leaves the top of the tank in a substantially dry, solvent-free condition.

It has been found that this particular printing or coat ing process is practical when the ink or coating composition is applied from a rotogravure or intaglio type cylinder which will usually be over-all etched or mechanically knurled. Because of the type of deposit laid down on the web from such a cylinder in the form of multitudinous fine dots, it is possible to flash off and recover practically all of the chlorinated solvent used as the vehicle. When the web being printed is a fibrous or absorptive material such as paper, the chlorinated solvent still vaporizes from the tiny dots before it becomes absorbed or picked up by the web. The deposit or coating which is applied by an etched or rotogravure cylinder is very uniform and by selecting the depth and screen size of the etching or knurling, the amount of the deposit or coating can be very closely controlled and accurately metered. The web being printed or coated travels at a fast speed which makes the process practical and economical Without requiring large and expensive drying equipment and tunnels such as commonly are used in connection with rotogravure printing employing expensive volatile solvents.

An important object of my invention is the provision of printing and coating compositions particularly suited for use in practicing the process and using the apparatus disclosed in my co-pending application Serial No. 846,750.

Another object of the invention are new and improved compositions for use in printing on smooth synthetic 3,303,160 Patented Feb. 7, 1967 films such as, polyethylene, polypropylene, polyvinyl and polyester films.

Another object of my invention are printing and coating compositions for the class described which have a high content of nylon scrap or thread.

Another object of my invention are printing and coating compositions of the class described for use in making pressure sensitive adhesive tape.

Another object of my invention are printing and coating compositions of the class described for use in making one-time carbon paper.

Another object of my invention are electrically conductive printing and coating compositions of the class described.

Another object of my invention are magnetic printing and coating compositions of the class described.

Another object of my invention are printing and coating compositions of the class described for use on metal foils.

Still another object of my invention are printing and coating compositions of the class described for printing on cellulose acetate and Mylar polyester films.

Certain other objects of the invention will, in part, be obvious and will in part appear hereinafter.

For a more complete understanding of the nature and scope of my invention, reference may now be had to the following detailed description thereof, wherein illustrative examples and embodiments are set forth.

An ink composition suitable for dissolving in a chlorinated or chlorinated-fluorinated solvent to make a bath to be used in practicing the process and using the apparatus disclosed in my co-pending application Serial No. 846,750 to print on polyethylene film is set forth in the following example:

EXAMPLE 1 Parts by weight Chlorinated rubber (67% chlorine) 7.00 Butadiene-acrylonitrile copolymer (Paracril C) 7.00 Methyl abiatate (Abalyn-Hercules) 4.65 Diallyl phthalate 4.65 2,2'-methylene bis (4-methyl-6-tert butylphenol) antioxidant 2246 American Cyanamid 0.07 Toluidene red (pigment) 11.60

The foregoing ink formulation may be prepared in a ball mill or in a colloid mill in acordance with known ink-making techniques. Approximately 35 parts of the ink formulation are dissolved in 65 parts of chlorinated solvent, preferably trichloroethylene. Other chlorinated solvents which may be used include perchloroethylene, pentachloroethylene, ethylene dichloride, trichloromethane, dichloromethane and methylene dichloride. Com mercial grade chlorinated solvents may be used alone or in suitable mixtures.

Chlorinated-fiuorinated solvents may also be used including trichlorotrifiuoroethane and trichloromonofluoromethane.

The ink formulation of Example 1 may be varied in several respects.

While the chlorinated rubber and butadiene-acrylonitrile copolymer is a preferred resin combination, either of these may be used alone and other synthetic rubber polymers and copolymers and resins soluble in chlorinated or chlorinated-fluorinated solvents may be employed, e.g., styreneisobutylene co polymer. Likewise, methyl abietate and diallyl phthalate is a preferred plasticizer combination, but other compatible plasticizers may be used. Other antioxidants for protection against heat or actinic light may also be used as Well as other pigments. Also dyes which are soluble in chlorinated or chlorinated-fluorinated solvents may be used in place of pigments, if desired.

Another ink formulation which is particularly adapted for printing on polyethylene is the following:

The nylon is dissolvedin the cresylic acid and then the pigment is milled in. Approximately 110 parts of the mixture are added to 90 parts of chlorinated solvent (trichloroethylene) so as to make up a bath suitable for use in the bottom of the fountain.

N-onylphenol may be used in place of the cresylic acid, and other than white or clear inks still bottoms may be used as the source of nonylphenoL. Other pigments may be used for different colors.

Still another ink-chlorinated solvent formulation for printing on polyethylene film according to the present invention is the following:

EXAMPLE 3 Parts by weight Chlorosulfonated polymer of ethylene (Hypalon Phenolic-maleic acid ester resin (Super Beckacite 100l-Reichold) 20 Chlorinated biphenyl (Arochlor) 20 The following is a suitable formulation for an adhesive composition for manufacturing pressure sensitive adhesive tape:

EXAMPLE 4 Parts by weight Methyl abietate 15 Alpha-methylstyrene polymer (Dow Resin 276 V2) l5 Hydrogenated rosin (Staybelite Ester lO-Hercules) l5 Chlorinated rubber (67% chlorine) l5 2,2'-methylene bis (4-methyl-6-tertiary butylphenol)- heat and light stabilizer 2 ing application Serial No. 846,750 is shown in the following example:

'EXAMPLE 5 l V V 7 Parts by V a weight Armid O (steam-amide 6%, oleamide 91%, linoleamide 3%) 30 Sugar cane wax 30 Chlorinated parafiin 5 Carbon black v l Aliz-a-rine Blue 1 2,2'-methylene bis (4-methyl-6-tertiary butyllphenol) 1 This formulation can be ball milled or milledin 'a colloid mill and 68 parts of the. ink can be dissolved in 32 parts of trichloroe'thylene to makeup a printing, or coating bath. 1

l The following formulation is specially adapted for application to aweb-or sheet for depositing thereon an electrically conductive coating:

EXAMPLE 6 V 7 Parts by weight Acetylene carbon black 25 Chlorinated parafiin 20 Methyl albietate 20 Lithium nitrate (or lithium chloride) l0 Seventy-five parts of this ink composition may be dissolved in 25 parts of chlorinated solvent to prepare a fountain bath which may be applied in accordance with the method of operation, and by the apparatus, disclosed in application Serial No. 846,750 to provide printed circuits, printed dry cells and various electrical circuitry.

The following is an example of a magnetic coating composition which may be applied to paper or other sheet material:

EXAMPLE 7 Parts by weight Carbonyl iron powder (or any iron oxide powder) 25 Chlorinated paraffin 25 Methyl abietate 25 Seventy-five parts of this formulation may be dissolved in 25 parts of chlorinated solvent and used as the fountain bath in the apparatus disclosed in Serial No. 846,- 750. After application to a sheet or Web the resulting coating may be magnetized.

The following formulation is particularly suitable for use in printing metal foil (e.g. aluminum foil) by the process and apparatus described in my application Serial No, 846,750.

EXAMPLE 8 V Parts by weight Ethyl cellulose (low viscosity) 2O Alpha-methylstyrene polymer (Dow Resin 276-V2) 10 Methyl abietate 10 A20 Oil Blue B 5 Forty-five parts of this formulation are dissolved in parts of trichloroethylene or other chlorinated solvent and used as the fountain solution in the apparatus.

The following ink composition in chlorinated solvent EXAMPLE 9 Parts by weight Ethylene dichloride 45 Methylmethacrylate (Plexiglas) 45 Glacial acetic acid l0 TiO pigment l0 Chlorinated or chlorinated-fiuorinated solvents are used in this process fora number of reasons. They vaporize readily at temperatures between about 75 F. to 160 F.

. into vapors which are mueh heavier than air so as to settle into the bottom of the condenser units.

These vapors condense easily and if desired for use in other formulationsmay be readily reclaimed by distilling and condensing; Chlorinated or halogenated solvents are in the nature of dryfsolvents which do not wet or hydrate the webs even if the web happens 'to be a highly porous and absorptive material, or a highly hydrogen bonded material, such as newsprint. V solvents are heated to the temperatures used in this invention, they have very high dissolving or suspending capacities for materials used in the ink or coating compositions including resins, fillers and pigments. Such materials dissolve or disperse readily in chlorinated solvents to a much higher or greater extent than they can be dissolved or dispersed in ordinary solvents. This high solubility and dispersibility is due to the combined solvent power and the heat. In practice, resins, fillers and pigments and other materials which are used in the inks or When these chlorinated coating composition to be applied in accordance with the present invention are milled in the heated phase into or in the presence of hot chlorinated solvent. By following this procedure, it is possible to easily provide inks or coating compositions which contain up to as much as 50 to 60% solids. In the usual cold ink or coating compositions the solids content usually does not exceed 20% by weight.

Chlorinated and chlorinated-fluorinated solvents are non-polar and by the incorporation therein of various known anti-static chemicals or agents having anionic or cationic properties, they will serve to change or convert the polarity of a web such as newsprint from a negative charge to a positive charge while being printed or coated in accordance with this invention. The following antistatic chemicals or agents may be used:

(a) Arquad S-2C-50 Armour Chemical Co. (soya trimethyl ammonium chloride 50% and dimethyl dicocoammonium chloride 50%) (b) Resin amine D(dehydr0 abietylamine N-acetamide) (c) Cetyltrimethyl ammonium bromide (d) Cetyl pyridinium chloride (e) Lauryl pyridinium chloride (f) N-butylamine lactate N-N-butyl lactamide (g) Sapamine K.W.C. Ciba Co. (tertiary ammonium compound) (h) Dilauryl dipropyl ammonium bromide (i) N-soya-n-ethyl morpholinum ethosulfate (1) Polyoxyalkylene stearate (Atlas Powder C0. G-33- This conversion or change in electrical charge is facilitated by having the impression roll formed of Thiokol, Teflon, or silicone rubber materials which are loaded with acetylene black and/or graphite or molybdenum disulphide. By employing anti-static chemicals or agents in the chlorinated solvents and by also forming the impression roll of one of the anti-friction materials mentioned above, it is possible to eliminate or substantially prevent the wicking action normally associated with a pressure printing operation such as in involved in a rotogravure or rotogra'vure printing unit.

In view of the teaching contained in the fore-going examples, those skilled in the art will be able to make and use either the compositions specifically disclosed herein or such modified formulations as may be required for their needs without departing from the spirit and scope of the present invention.

6 This application is a continuation-in-part of my copending application Serial No. 846,750.

What is claimed as new is: I claim: An ink composition having substantially the following composition:

Parts by weight Nylon scrap Cresylic acid 30 Pigment 10 References Cited by the Examiner UNITED STATES PATENTS 2,279,771 4/ 1942 Austin 260-338 2,293,760 8/1945 Peters 260-338 2,381,753 8/1945 Irion 260-338 2,550,650 4/1951 Arnold 260-338 2,590,642 3/1952 Nichols 260-338 2,612,463 9/1952 Brown 260-338 2,633,456 3/1953 Vaughan 260-35 2,838,463 6/1958 Freeman 260-35 2,852,397 9/1958 Goessling 106-31 2,852,398 9/1958 Goessling 106-31 2,856,379 10/1958 Carnall 260-338 2,894,928 7/1959 Hohnstine 260-338 2,914,480 11/ 1959 Hagopian 25262.5 2,956,977 10/ 1960 Caldwell et a1. 260-312 2,979,471 4/ 1961 Sweeney 260-17 2,984,640 5/1961 Kaplan 260-334 2,989,492 6/1961 Sanderson 260-17 2,991,257 7/1961 Smith-Johannsen 252506 2,995,529 8/ 196 1 Smith-Johannsen 252506 3,003,965 10/1961 Troelstra et al 252-62.5 3,005,793 10/1961 Wagner 260-312 3,009,896 11/1961 Sattler et al. 260-33.4

OTHER REFERENCES Polyamide Resins (Floyd), Reinhold Corporation, New York, 1958, pages 72 and 75 and 210-213.

The Condensed Chemical Dictionary, 5th ed., Reinhold Corporation, New York, 1956, page 794.

MORRIS LIEBMAN, Primary Examiner. JULIUS GREENWALD, Examiner.

S. R. BRESCH. J. H. BEHRINGER, A. H. KOECKERT,

Assistant Examiners. 

